2-((1S,4S)-4-Carboxymethyl-cyclopent-2-enyl)-malonic acid diethyl ester | 83219-63-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 2-((1S,4S)-4-Carboxymethyl-cyclopent-2-enyl)-malonic acid diethyl ester
• CAS: 83219-63-0
• 化学式: C₁₄H₂₀O₆
• 分子量: 284.309
• InChiKey: IHRRNARXVRMLJF-VHSXEESVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  20.0
• 可旋转键数：
  7.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  89.9
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  乙醇 、 2-((1S,4S)-4-Carboxymethyl-cyclopent-2-enyl)-malonic acid diethyl ester 在 对甲苯磺酸 、 lithium chloride 作用下， 生成 cis-3,5-bis<(ethoxycarbonyl)methyl>cyclopentene
  参考文献：
  名称：

  Sequential (.pi.-allyl)palladium alkylations

  摘要：

  DOI：

  10.1021/jo00145a021
• 作为产物：
  描述：

  3,3a,4,6a-tetrahydro-2H-cyclopenta[b]furan-2-one 、 丙二酸二乙酯钠盐 在 四(三苯基膦)钯 作用下， 以 四氢呋喃 为溶剂， 以93%的产率得到2-((1S,4S)-4-Carboxymethyl-cyclopent-2-enyl)-malonic acid diethyl ester
  参考文献：
  名称：

  Scope and Limitations in Palladium-Catalyzed Substitution Reactions of Unsaturated Fused Lactones

  摘要：

  The palladium-catalyzed nucleophilic substitution of C-4-substituted 2-oxabicyclo[3.3.0]oct-7-en-3-ones (unsaturated, fused lactones) have been studied particularly in relation to how electronic and steric factors influenced the rate and efficiency of substitution reactions. Thus, a range of a-substituted lactones were prepared (X = H, Me, OH, OAc, Br, N-3, NHCBZ) and subjected to palladium-catalyzed substitution reaction with diethyl sodiomalonate, and it was found that reaction rates increased with increasing electron-withdrawing ability of the substituent and that there was a strong correlation between rate and pK(a) of the corresponding substituted acetic acids (XCH2-CO2H). The only exception to the correlation was with X = OH, in which case the endo isomer reacted considerably faster than expected and the exo isomer reacted much slower than expected. It was also found that the rates of reaction of the endo isomers were greater than the exo isomers. The increased rates have been accounted for by a shift in equilibrium between the lactone and the pi-allyl palladium intermediate toward the latter species due to the increased stability of the carboxylate (electronic effects) or relief of steric hindrance in the starting lactone. The scope and limitations of the palladium-catalyzed substitution reaction were studied by reacting a range of lactones with a range of nucleophiles. Lactones with unactivated leaving groups such as 2 (X = H) coupled efficiently with good nucleophiles such as malonate but only poorly with less reactive nucleophiles such as azide. Lactones with activated leaving groups such as 4a (X = OH) coupled efficiently with a broad range of nucleophiles.

  DOI：

  10.1021/jo962106b

文献信息

• Scope and Limitations in Palladium-Catalyzed Substitution Reactions of Unsaturated Fused Lactones
  作者：Varinder K. Aggarwal、Nuno Monteiro、Gary J. Tarver、Ray McCague

  DOI：10.1021/jo962106b

  日期：1997.7.1

  The palladium-catalyzed nucleophilic substitution of C-4-substituted 2-oxabicyclo[3.3.0]oct-7-en-3-ones (unsaturated, fused lactones) have been studied particularly in relation to how electronic and steric factors influenced the rate and efficiency of substitution reactions. Thus, a range of a-substituted lactones were prepared (X = H, Me, OH, OAc, Br, N-3, NHCBZ) and subjected to palladium-catalyzed substitution reaction with diethyl sodiomalonate, and it was found that reaction rates increased with increasing electron-withdrawing ability of the substituent and that there was a strong correlation between rate and pK(a) of the corresponding substituted acetic acids (XCH2-CO2H). The only exception to the correlation was with X = OH, in which case the endo isomer reacted considerably faster than expected and the exo isomer reacted much slower than expected. It was also found that the rates of reaction of the endo isomers were greater than the exo isomers. The increased rates have been accounted for by a shift in equilibrium between the lactone and the pi-allyl palladium intermediate toward the latter species due to the increased stability of the carboxylate (electronic effects) or relief of steric hindrance in the starting lactone. The scope and limitations of the palladium-catalyzed substitution reaction were studied by reacting a range of lactones with a range of nucleophiles. Lactones with unactivated leaving groups such as 2 (X = H) coupled efficiently with good nucleophiles such as malonate but only poorly with less reactive nucleophiles such as azide. Lactones with activated leaving groups such as 4a (X = OH) coupled efficiently with a broad range of nucleophiles.
• Sequential (.pi.-allyl)palladium alkylations
  作者：Richard S. Valpey、David J. Miller、James M. Estes、Stephen A. Godleski

  DOI：10.1021/jo00145a021

  日期：1982.11